Alejandro Pérez Castorena 1

UncertaintyTRACE METALS MEASUREMENT, USING

HR ICP-MS

Alejandro Pérez Castorena 2

PREPARATION OF THE WORKING STANDARD SOLUTION (Multielemental)

PREPARATION OF THE CC STANDARD (S1)

PREPARATION OF THE SINGLE ELEMENT, INTERNAL STANDARDS

PREPARATION OF THE MULTIELEMENTAL INTERNAL STANDARD SOLUTION (Ga, Rh and Bi) and CALIBRATION CURVE

Working standard solutionSINGLE ELEMENT

HNO3

3 %

CRM´s

1

2

3

5...

+

5

3

2

1

...

Cd2(Cu)

)(DMRCu

1

Cd1(Cu)

5

...

CM(Cu)CM(Pb)CM(Ni)CM(Zn)...CM(Ba)

CM(Ga)CM(Rh)CM!(Bi)

Alejandro Pérez Castorena 3

Standard preparationSensitivity

Internal standardpreparation, C

Reproducibilityof the measurement

Density of the sample

Atomic weight

Cm

Step VIIIStep VII

Intensity of the Blank

IUPAC

StdIS

ISStd

CICI

S

22

36)(

resolutions

u d

C

Balance

linearity

repeatability

Balance

linearity

repeatability

resolution

measurement

2222222

1

1)()()(

)()()()(

)()()(

AAu

CRuu

GaCGaCu

IIu

SSu

CuCCuCu

Csampleu

sampledM

dM

Blank

Blank

S

S

sample

C

5)( sen sitivity

sSu

Alejandro Pérez Castorena 4

Contribution to the measurement result

0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007

S

C(Std)

IB

C(IS)

fd(sample)

R

Density

A

Co

ntr

ibu

tio

n

Relative uncertainty

Description Value Units Source of information

Original uncertainty

Units Type of distribution

Relative uncertainty

S Sensitivity 0.69 - 0.004 - A, normal 0.006C(Std) Preparation of the

standard0.0433 mg/kg 0.0001 mg/kg B, normal 0.0030

IB Intensity of the blank 93849.4 cps experimental 22.5 cps A, normal 2.4E-04

C(IS) Internal standard preparation (Ga)

0.60089 mg/kg Calculated from experimental data

0.000902 mg/kg B, normal 0.00150

fd(sample) Dilution factor of the sample

7.7957 experimental 0.00003 B, normal 0.0000040

R Reproducibility of the sample measurement

0.2092 mg/Kg experimental 0.0004 mg/Kg A, normal 0.0018

Density Density 1.0015 g/L experimental 2.4256E-06 g/L A, normal 2.4220E-06A Atomic weight 63.546 g/mol 0.003 g/mol B, normal 4.721E-05

Sample concentration

0.210 mg/L uC 0.007 mg/L

Sample concentration

3.297E-06 mol/L uC 2.30E-08 mol/L

K 2 3.297E-06 ± 4.59E-08 mol/L

1.00E+00 mol 3297 ± 46 nmol/L

1.00E+09 nmol Ur 1.4 %

Alejandro Pérez Castorena 5

PREPARATION OF THE WORKING STANDARD (SINGLE ELEMENT SOLUTION)

Cd2(Cu)

)(DMRCu)(

)(

1 CuW

CRMW

d

Cu

)()()(

11 CuW

CRMWDMRCC

d

Cud

)(

)(

2

1

CuW

CW

d

dCu

)(

)(

2

112 CuW

CWCC

d

dCudd

)()()()()(

)(21

12 CuWCuW

CWCRMWCRMCCuC

dd

dCuCud

)(DMRCu)(CRMWCu)(1 CuWd

)( 1dCu CW )(2 CuWd

linearity

repeatability

linearity linearity

repeatability repeatability

linearity

repeatability

certificate

2

2

2

2

1

1

2

1

1

22

2 )())((

)())((

)())((

)())((

)())((

)(

CuWCuWu

CuWCuWu

CWCWu

CRMWCRMWu

CRMCCRMCu

CuCu

d

d

d

d

dCu

dCu

Cu

Cu

d

C

I III IVII

Alejandro Pérez Castorena 6

PREPARATION OF THE WORKING STANDARD SOLUTION (Multielemental)

CM(Cu)CM(Pb)CM(Ni)CM(Zn)...CM(Ba)

)(2 CuCd)( 2dCu CW

MW

linearity

repeatability

linearity

repeatability

)(2 CuCdM

dCu

W

CW )( 2

M

dCudM W

CWCuCCuC

)()()( 22

22

2

2

2

2

2)(

)())((

)())((

)(

M

M

dCu

dCu

d

d

M

C

WWu

CWCWu

CuCCuCu

CuCu

V VI

IV

Alejandro Pérez Castorena 7

PREPARATION OF THE CC STANDARD (S1)

CS1(Cu)CS!(Pb)CS!(Ni)CS!(Zn)...CS!(Ba)

)(CuWM

1dSW

linearity

repeatability

linearity

repeatability

)(CuCM

1

)(

dS

M

W

CuW

1

1

)()()(

dS

MMM

S WCWCuC

CuC

2

1

1

22

1

)(

)())((

)())((

)(

dS

dS

MM

MM

M

M

S

C

W

Wu

CWCWu

CuCCuCu

CuCu

VII VIII

)(CuCM VI

Alejandro Pérez Castorena 8

PREPARATION OF THE SINGLE ELEMENT, INTERNAL STANDARDS

Cd2(IE)

)(CRMIE)(

)(

1 GaW

IEW

d

Ga

)(

)()(

11 GaW

IEWIECC

d

Gad

)(

)(

2

1

GaW

CW

d

dGa

)(

)(

2

112 GaW

CWCC

d

dGadd

)()()()()(

)(21

12 GaWGaW

CWIEWIECGaC

dd

dGaGad

)(CRMIE)(IEWGa)1(dWGa

)(1 Gad CW )(2 GaWd

linearity

repeatability

linearity linearity

repeatability repeatability

linearity

repeatability

certificate

2

2

2

2

1

1

2

1

1

22

2 )())((

)())((

)())((

)())((

)())((

)(

GaWGaWu

GaWGaWu

CWCWu

IEWIEWu

IECIECu

GaCu

d

d

d

d

dGa

dGa

Ga

Ga

d

C

I IVIIIII

Alejandro Pérez Castorena 9

PREPARATION OF THE MULTIELEMENTAL INTERNAL STANDARD SOLUTION (Ga, Rh and Bi) and CC

)(2 GaCd)( 2dGa CW

MW

linearity

repeatability

linearity

repeatability

M

dGa

W

CW )( 2

M

dGadM W

CWGaCGaC

)()()( 22

22

2

2

2

2

2 )()())((

)())((

)(

M

M

dGa

dGa

d

d

M

C

WWu

CWCWu

GaCGaCu

GaCu

V VI)(2 GaCd

CM(Ga)CM(Rh)CM!(Bi)

dM

M

W

GaW )(

dM

MM

dM WGaWGaC

GaC)()(

)(

222

)())(()())((

)(

dM

dM

dM

M

M

M

dM

C

WWu

WGaWu

GaCGaCu

GaCu

VII

VIII

CdM(Ga)CdM(Rh)CdM!(Bi)